Reaction of the non-substituted/substituted unsymmetric pinene-derived complex[Pt(N^C^N')Cl]with the aryl isocyanide 2,6-dimethylphenyl isocyanide(CNXyl)afforded a mixture of two isomeric species:the ionic complex...Reaction of the non-substituted/substituted unsymmetric pinene-derived complex[Pt(N^C^N')Cl]with the aryl isocyanide 2,6-dimethylphenyl isocyanide(CNXyl)afforded a mixture of two isomeric species:the ionic complex[Pt(κ^(3)-N^C^N')(CNXyl)]Cl([A]Cl)and the molecular complex[Pt(κ^(2)-N^C^N')(CNXyl)Cl](B).Isomer B was almost the dominating product.The structures of the isomer B derivatives bearing-CF_(3)and-Cl substituents on the pyridine ring of the pinene moiety(5B and 7B,respectively)have been confirmed by single-crystal X-ray diffraction,revealing a slightly distorted square planar geometry with trans-N_(N^C^N'),CNR configuration(The terminal N atom of theκ^(2)-N^C^N'ligand is trans to the isocyanide ligand CNXyl.).Isomer B is thermodynamically more stable,as confirmed by theoretical calculations.CCDC:2416415,5B;2416414,7B.展开更多
In this work,we synthesize two luminescent Pt(Ⅱ)complexes using differentπ-conjugated bidentate ligands.Both complexes are assembled into three-dimensional(3D)networks through non-classical intermolecular interactio...In this work,we synthesize two luminescent Pt(Ⅱ)complexes using differentπ-conjugated bidentate ligands.Both complexes are assembled into three-dimensional(3D)networks through non-classical intermolecular interactions in the crystal state.Unexpectedly,substituting pyridine with the more extensivelyπ-conjugated quinoline significantly increases the dihedral angles between the phenyl and quinolyl groups of the bidentate ligands.This alteration disrupts theπ-πinteractions between molecules,resulting in distinct optical properties upon exposure to external stimuli.By integrating these complexes into polymers,we fabricate electrospun films containing luminescent nanofibers that exhibit reversible optical changes.These findings have paved the way for the development of high-performance optical encryption and anti-counterfeiting materials,achieved through the employment of simple chromophores.展开更多
The interactions between human erythrocyte spectrin(SP) and Pt(II) complexes with different composition and configuration were studied by fluorescence and circular dichroism spectra. The results showed that there are ...The interactions between human erythrocyte spectrin(SP) and Pt(II) complexes with different composition and configuration were studied by fluorescence and circular dichroism spectra. The results showed that there are 4.7×10 2 binding sites of cisplatin(CDDP) in a spectrin tetramer(SPT). Among them, about 70 sites with apparent binding constant K 1】3.47×10 6 were of highest affinity, 1.8×10 2 sites with K 2 = 3.47×10 6 were of high affinity, and other 2.2×10 2 sites with K 3 = 8.77×10 5 were of low affinity. The conformation change of spectrin, depending on the concentration of Pt(II) complex and molar ratio(R) of Pt(II) complex to spectrin, was induced by the binding of Pt(II) complexes. It indicated that the interaction of both CDDP and cis diaquodiamine platinum(DADP) with SP followed a two step first order kinetic process in the first stage (1 h), and the kinetic constants were determined. In the second stage, the induced conformation change, polymerization and depolymerization of SP were probably involved. It was noticed that in the reaction of SP and Pt(II) complexes with 1,2 cyclohexanediammine isomers as chiral carrier ligand, stereo matching played a more important role than the affinity of Pt(II) to thiol groups of SP.展开更多
A novel cationic Pt(Ⅱ)complex 2 with 2-(2,4-difluorophenyl)pyridine as the cyclometalating ligand and 1,10-phenanthroline as the auxiliary ligand has been synthesized and fully characterized.This complex exhibits muc...A novel cationic Pt(Ⅱ)complex 2 with 2-(2,4-difluorophenyl)pyridine as the cyclometalating ligand and 1,10-phenanthroline as the auxiliary ligand has been synthesized and fully characterized.This complex exhibits much higher aggregation-induced phosphorescent emission activity than that of a nonfluorinated complex 1 in CH_(3)CN/H_(2)O.The complex 2 demonstrates efficient detection on picric acid(PA)in CH_(3)CN/H_(2)O,providing a high quenching constant(K_(SV)=2.3×10^(4) L/mol)and a low limit of detection(LOD=0.26μmol/L).In addition,complex 2 shows high selectivity for detection of PA in real water samples.Density functional theory calculations and proton nuclear magnetic resonance spectra suggest that the detection mechanism is attributed to the photo-induced electron transfer.展开更多
Treatment of precious metals in electronic waste has attracted tremendous attention and is essential for both environmental protection and resource sustainable development.In this study,a novel adsorbent for precious ...Treatment of precious metals in electronic waste has attracted tremendous attention and is essential for both environmental protection and resource sustainable development.In this study,a novel adsorbent for precious metal ions,V_(2)O_(3)spiny hollow nanospheres(pV_(2)O_(3)SHN),was synthe sized through a one-step hydrothermal-as sis ted methodology for the adsorption of Au(Ⅲ),Ag(Ⅰ),Pd(Ⅱ),and Pt(Ⅳ) from the leaching solution of electronic waste.The results reveal that the p-V2O3SHN hierarchy was successfully constructed with a hollow structure and dense spiny morphology.The prepared p-V2O3SHN can effectively remove precious metal ions such as Au(Ⅲ),Ag(Ⅰ),Pd(Ⅱ),and Pt(Ⅳ),with the selective capture order being Au(Ⅲ)> Ag(Ⅰ)> Pt(Ⅳ)> Pd(Ⅱ)> other metal ions.This superior adsorption capability can be attributed to the multi-diffusible,intermingled composition,and numerous active sites decorating the p-V2O3SHN hierarchy,facilitating the uptake of Au(Ⅲ),Ag(Ⅰ),Pd(Ⅱ),and Pt(Ⅳ) ions from electronic waste.The Langmuir model provided a better fit for the uptake process,revealing maximum uptake capacities of 833.33 mg/g for Au(Ⅲ),370.37 mg/g for Ag(Ⅰ),42.01 mg/g for Pd(Ⅱ),and 77.51 mg/g for Pt(Ⅳ) on p-V_(2)O_(3)SHN.Remarkably,p-V_(2)O_(3)SHN exhibited a robust affinity for the adsorbate due to the presence of surface defects and reduction reactions.The new p-V2O3SHN also demonstrated good reusability for three sorption cycles,highlighting its potential for electronic waste treatment.Due to its facile synthesis and excellent efficiency,hierarchical p-V2O3SHN presents itself as a promising candidate for the selective uptake of Au(Ⅲ),Ag(Ⅰ),Pt(Ⅳ),and Pd(Ⅱ) from electronic waste.展开更多
The title complex, [Mn2(O-Py3A)(DPK-CH3O)(CH3OH)]2?2ClO4?4CH3OH (C64H70Cl2- Mn4N12O22, Py3AH = N-(bis(2?-pyridyl)methyl)-2-pyridinecarboxamide, DPK = di-2-pyridyl ketone) has been synthesized and its crystal structu...The title complex, [Mn2(O-Py3A)(DPK-CH3O)(CH3OH)]2?2ClO4?4CH3OH (C64H70Cl2- Mn4N12O22, Py3AH = N-(bis(2?-pyridyl)methyl)-2-pyridinecarboxamide, DPK = di-2-pyridyl ketone) has been synthesized and its crystal structure was determined by X-ray diffraction. It crystallizes in the monoclinic system, space group P21/n with a = 12.667(9), b = 16.793(12), c = 17.070(13) ?, β = 100.997(13)o, V = 3565(5) ?3, Dc = 1.537 g/cm3, Mr = 1649.98, Z = 2, μ(MoKα) = 0.851 mm-1 and F(000) = 1696. The final R and wR are 0.0639 and 0.1320, respectively for 3979 observed reflec- tions with I > 2σ(I). In the tetranuclear complex, each Mn(II) atom is six-coordinated and the four Mn(II) atoms are coplanar, exhibiting a parallelogram arrangement; while the deprotonated ligands are oxidized to O-Py3A2- anions and cleaved to DPK-CH3O– anions (the monoanion of mono- methylated diol of DPK) furthermore.展开更多
The Cu(II) complex with the ligand 2,9-bis(n-2?5?diazaheptanyl)-1,10-phenan- throline (L) has been synthesized and characterized by single-crystal X-ray diffraction. It crys- tallizes in the monoclinic system, space g...The Cu(II) complex with the ligand 2,9-bis(n-2?5?diazaheptanyl)-1,10-phenan- throline (L) has been synthesized and characterized by single-crystal X-ray diffraction. It crys- tallizes in the monoclinic system, space group P21/n with a = 12.549(4), b = 13.544(4), c = 16.767(5) ? = 107.179(5), C22H32Cl2N6CuO8, Mr = 642.98, V = 2722.5(13) 3, Z = 4, Dc = 1.569 g/cm3, ?= 1.056 mm-1, F(000) =1332, the final R = 0.0733 and wR = 0.1581. The X-ray analysis revealed that the Cu(II) ion is coordinated by six nitrogen atoms of the ligand, in which two nitrogen from phenanthroline and another two from the imine groups near phenanthroline are in the equatorial plane while the two from imine groups at the end of both arms in the axial positions. The coordination geometry can be described as a compressed octahedron.展开更多
The platinum (II) complexes of the [Pt (N4,N7-Ribavirin) (DMSO) Cl], [Pt (N4,N7-De-oxyribavirin) (DMSO) Cl] were obtained by the reactions of cis-[Pt (DMSO)2 Cl2] and K[Pt (DMSO) Cl3] with 1-??-D-ribofuranosyl-1,2,4-t...The platinum (II) complexes of the [Pt (N4,N7-Ribavirin) (DMSO) Cl], [Pt (N4,N7-De-oxyribavirin) (DMSO) Cl] were obtained by the reactions of cis-[Pt (DMSO)2 Cl2] and K[Pt (DMSO) Cl3] with 1-??-D-ribofuranosyl-1,2,4-triazole-3-carboxamide (Ribavirin) and its deoxy-analogue (deoxyribavirin). The preparation of 1-(2'-deoxy-?-D-ribofuranosyl) -1,2,4-triazole-3-carboxamide was also performed through a four-step procedure, protection of 3', 5'-dihydroxyl group of Ribavirin with 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane (TPDS-Cl), phenoxythio-carbonylation of the 2'-hydroxyl group of 3', 5'-O-TPDS-Ribavirin with phenoxythiocarbonyl-chloride (PTC-Cl), reduction of 2′-O-phenoxythiocarbonyl ester of 3', 5'-O-TPDS-Ribavirin with tri-n-butyltin hydride and AIBN, deprotection of 3', 5'-O-TPDS-Ribavirin with tetrabutylammon-ium fluoride in THF.展开更多
An alkaline earth metal-organic framework [Ba（Hsip）（H2O）4]n （1, NaH2sip = 5-sulfoisophthalic acid sodium） has been constructed, and characterized by single-crystal X-ray diffraction. In complex 1, each Ba（II） ...An alkaline earth metal-organic framework [Ba（Hsip）（H2O）4]n （1, NaH2sip = 5-sulfoisophthalic acid sodium） has been constructed, and characterized by single-crystal X-ray diffraction. In complex 1, each Ba（II） atom coordinates to one ligand Hsip3- and four water molecules with a distorted nine-coordinated monocapped tetragonal antiprism geometry. Each Hsip2- anion acts as a μ3-bridging ligand, in which two carboxylate groups adopt the same bidentate chelating coordinating model and the sulfonate group takes a monodentate coordinating model, resulting in a wave-like two-dimensional network with a （6, 3） topological structure. The two-dimensional networks are further linked by O–H···O to form a three-dimensional structure. Luminescent property and thermal stability of complex 1 are investigated. 1 belongs to the orthorhombic system, space group Pna21 with a = 7.3333（2）, b = 16.7044（3）, c = 10.4817（2）, Z = 4, V = 1283.99（5）3, Mr = 453.58, Dc = 2.346 g/cm3, F（000） = 880, μ = 3.314 mm–1, the final R = 0.0261 and wR = 0.0592 for 2425 observed reflections with I 2σ（I）.展开更多
Oxygenation constants and thermodynamic parameters DeltaH degrees and DeltaS degrees of cobalt (II) complexes with bis-(furaldehyde) Schiff bases (1, 2, 3, 4)were obtained by mearsuring saturated dioxygen uptake of th...Oxygenation constants and thermodynamic parameters DeltaH degrees and DeltaS degrees of cobalt (II) complexes with bis-(furaldehyde) Schiff bases (1, 2, 3, 4)were obtained by mearsuring saturated dioxygen uptake of these complexes in pyridine at different temperature. These complexes could activate molecular oxygen and were used as catalysts in cyclohexene oxidation. The influence of ligand structure on the dioxygen affinity and catalytic activity of the complexes were discussed.展开更多
The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2?-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was det...The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2?-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was determined by single-crystal X-ray diffraction method. It crys- tallizes in triclinic, space group P1, C44H31ClCu2N4O12, Mr = 970.26, a = 8.175(2), b = 16.254(4), c = 16.946(4) ?, α = 62.966(6), β = 84.833(8), γ = 84.348(8)°, V = 1993.4(8) ?3, Z = 2, Dc = 1.616 g/cm3, F(000) = 988 and μ = 1.207 mm-1. The final R = 0.0429 and wR = 0.0843 for 5682 observed reflections with I > 2σ(I). Each copper(II) atom displays a distorted square-pyramidal geometry with two nitrogen atoms of one chelate 2,2?-bipy molecule, two oxygen atoms from two different bridging carboxylate groups of Hpht- and one bridging chloride atom occupying the apical position. The two copper(II) atoms are connected by a μ2-Cl atom and two bridging Hpht- ligands in a syn-syn coordination mode to form an isolated dinuclear unit. The molecular structure is extended to a one-dimensional wavy chain through hydrogen bonds. The title complex exhibits blue fluorescent emission at 443 nm (λex = 372 nm) in the solid state at room temperature.展开更多
A new metal-organic complex Zn2（cbba）4（phen）2 （Hcbba = 2-（4＇chlorine-ben- zoyl）benzoic acid, phen = 1,10-phenanthroline） 1 has been hydrothermally synthesized and structurally characterized by elemental analy...A new metal-organic complex Zn2（cbba）4（phen）2 （Hcbba = 2-（4＇chlorine-ben- zoyl）benzoic acid, phen = 1,10-phenanthroline） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence spectrum and single-crystal X-ray diffraction. The compound crystallizes in orthorhombic, space group Pbcn with a = 12.0821（II）, b = 18.3140（17）, c = 30.961（3） A, V= 6850.7（11） A^3, C80H48C14N4O12Zn2, Mr= 1529.76, Dc = 1.483 g/cm^3,μ（MoKa） = 0.925 mm^-1, F（000） = 3120, Z = 4, the final R = 0.0559 and wR = 0.1146 for 3963 observed reflections （I〉 2σ（I））. In the crystal structure, the zinc atom is five-coordinated with three carboxylate oxygen atoms from three different cbba ligands and two nitrogen atoms from the phen ligand, showing a distorted square-pyramidal geometry. Furthermore, it exhibits a 3D supramolecular network through π-π interactions and shows yellow photoluminescent property at room temperature.展开更多
A new mixed-ligand nickel（Ⅱ） complex, [Ni（L）（DCA）（H2O）]·2H2O （L = C8H9N3, 2-aminomethyl-benzimidazole, DCA2- = 7-oxabicyclo[2,2,1]heptane-2,3-dicarboxylate, demethylcantharate, C8H8O5）, has been synthe...A new mixed-ligand nickel（Ⅱ） complex, [Ni（L）（DCA）（H2O）]·2H2O （L = C8H9N3, 2-aminomethyl-benzimidazole, DCA2- = 7-oxabicyclo[2,2,1]heptane-2,3-dicarboxylate, demethylcantharate, C8H8O5）, has been synthesized and characterized. The structure of the complex was determined by single-crystal X-ray diffraction. It is of monoclinic system, space group P21/c with a = 7.7211（7）, b = 12.0799（12）, c = 19.7867（19）, β = 100.390（6）°, V = 1815.2（3） nm3, Dc = 1.625 g·cm-3, Ζ = 4, F（000） = 928, R = 0.0314 and wR = 0.0822. In addition, the interaction between the complex and DNA was studied by means of fluorescence spectra and viscosity. The results indicate that the complex binds to DNA by the mode of partial intercalation with the Stern-Volmer constants Ksv of 3.81 × 104 mol·L-1.展开更多
A convenient and efficient method for the preparation of α-substituted β-amino acids has been developed by reacting compound 2 with various boric acid/borate 3 through Suzuki coupling reaction,which gave multiple st...A convenient and efficient method for the preparation of α-substituted β-amino acids has been developed by reacting compound 2 with various boric acid/borate 3 through Suzuki coupling reaction,which gave multiple structure types of substituted Ni（II） complexes 4 in high yields.Hydrogenation and hydrolysis of complexes 4 led to the corresponding α-substituted β-amino acids.展开更多
A new zinc(II) complex, Zn(2-NH2py)2Br2 (py=pyridine), has been synthesized, and its molecular structure has been confirmed by IR, elemental analysis and -ray crystal structure analysis. Its space group is P21/n with...A new zinc(II) complex, Zn(2-NH2py)2Br2 (py=pyridine), has been synthesized, and its molecular structure has been confirmed by IR, elemental analysis and -ray crystal structure analysis. Its space group is P21/n with Mr=413.43 (C10H12Br2N4Zn), a=7.435(2), b=12.865(3), c=14.186(4)? b=94.08(2)? V=1353.5(5) 3, Z=4, Dc=2.029 g/cm3, F(000)=328, ?2.378mm－1, R=0.0283, wR=0.0501. The total observed reflections with I≥2?I) were 5314, of which the independent reflections were 3106. The complex structure contains a distorted tetrahedron formed by four atoms coordinated to zinc atom, namely two bromide atoms and two nitrogen atoms. The two ZnBr bond lengths within one molecule, 2.3763(6) and 2.4002(5)? respectively, are not equal; and so are the two ZnN bond lengths, which are 2.031(2) and 2.044(2)?respectively. The calculation results using PM3 method through MOPAC software package in Chem 3D show that its first molecular hyperpolarizability b value is 5.210－30esu, which is comparable with that of p-nitroaniline. No bulk SHG effect has been detected due to the centrosymmetric space group.展开更多
A new dinuclear complex [Zn（dpa）（bipy）（H2O）]2 （dpa = 2,2＇-diphenic acid, bipy = 2,2＇-bipyridine） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence s...A new dinuclear complex [Zn（dpa）（bipy）（H2O）]2 （dpa = 2,2＇-diphenic acid, bipy = 2,2＇-bipyridine） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence spectrum and single-crystal X-ray diffraction. The complex crystallizes in monoclinic, space group P21/c with a = 10.960（2）, b = 9.4841（18）, c = 20.599（4）, β = 104.452（3）o, V = 2073.4（7）3, C48H36N4O10Zn2, Mr = 959.55, Dc = 1.537 g/cm3, μ（MoKα） = 1.225 mm-1, F（000） = 984, Z = 2, the final R = 0.0364 and wR = 0.0843 for 2788 observed reflections （I 〉 2σ（I））. In the crystal structure, the zinc atom is five-coordinated with two carboxylate oxygen atoms from different dpas, one coordinated water molecule and two nitrogen atoms from bipy ligands, showing a slightly distorted triangular bipyramidal geometry. Furthermore, it exhibits a zero-dimensional network structure with a sixteen-membered ring and shows yellow photoluminescent property at room temperature.展开更多
A new copper complex 2{Cu（C10H8N2）[C8H11O2（COO）]（H2O）3}·（H2O）5 with bicycle[2.2.1]hept-2-en-5,6-dicarboxylic acid（H2L） [C7H8（COOH）2], basic copper carbonate and 2,2＇-bipyridine has been synthesized i...A new copper complex 2{Cu（C10H8N2）[C8H11O2（COO）]（H2O）3}·（H2O）5 with bicycle[2.2.1]hept-2-en-5,6-dicarboxylic acid（H2L） [C7H8（COOH）2], basic copper carbonate and 2,2＇-bipyridine has been synthesized in the mixed solvents of methanol and water. It crystallizes in the triclinic system, space group P1, with a = 7.4626（5）, b = 11.9779（8）, c = 12.9841（8）A, α = 109.7040（10）, β = 98.7550（10）, γ = 90.6240（10）°, V = 1077.50（12）A3, Dc = 1.538 g/cm^3, Z = 1, F（000） = 520, GOOF = 1.065, R = 0.0360 and wR = 0.0950. The copper ion is coordinated with four oxygen atoms from one H2 L molecule and three water molecules together with two nitrogen atoms from the 2,2＇-bipyridine molecule, forming a distorted octahedral coordination geometry. The thermal stability and electrochemical properties were also studied.展开更多
文摘Reaction of the non-substituted/substituted unsymmetric pinene-derived complex[Pt(N^C^N')Cl]with the aryl isocyanide 2,6-dimethylphenyl isocyanide(CNXyl)afforded a mixture of two isomeric species:the ionic complex[Pt(κ^(3)-N^C^N')(CNXyl)]Cl([A]Cl)and the molecular complex[Pt(κ^(2)-N^C^N')(CNXyl)Cl](B).Isomer B was almost the dominating product.The structures of the isomer B derivatives bearing-CF_(3)and-Cl substituents on the pyridine ring of the pinene moiety(5B and 7B,respectively)have been confirmed by single-crystal X-ray diffraction,revealing a slightly distorted square planar geometry with trans-N_(N^C^N'),CNR configuration(The terminal N atom of theκ^(2)-N^C^N'ligand is trans to the isocyanide ligand CNXyl.).Isomer B is thermodynamically more stable,as confirmed by theoretical calculations.CCDC:2416415,5B;2416414,7B.
基金supported by the National Natural Science Foundation of China(Nos.22201057 and 22472044)Zhejiang Provincial Natural Science Foundation of China(Nos.LR22B010001 and LQ23B010001)。
文摘In this work,we synthesize two luminescent Pt(Ⅱ)complexes using differentπ-conjugated bidentate ligands.Both complexes are assembled into three-dimensional(3D)networks through non-classical intermolecular interactions in the crystal state.Unexpectedly,substituting pyridine with the more extensivelyπ-conjugated quinoline significantly increases the dihedral angles between the phenyl and quinolyl groups of the bidentate ligands.This alteration disrupts theπ-πinteractions between molecules,resulting in distinct optical properties upon exposure to external stimuli.By integrating these complexes into polymers,we fabricate electrospun films containing luminescent nanofibers that exhibit reversible optical changes.These findings have paved the way for the development of high-performance optical encryption and anti-counterfeiting materials,achieved through the employment of simple chromophores.
文摘The interactions between human erythrocyte spectrin(SP) and Pt(II) complexes with different composition and configuration were studied by fluorescence and circular dichroism spectra. The results showed that there are 4.7×10 2 binding sites of cisplatin(CDDP) in a spectrin tetramer(SPT). Among them, about 70 sites with apparent binding constant K 1】3.47×10 6 were of highest affinity, 1.8×10 2 sites with K 2 = 3.47×10 6 were of high affinity, and other 2.2×10 2 sites with K 3 = 8.77×10 5 were of low affinity. The conformation change of spectrin, depending on the concentration of Pt(II) complex and molar ratio(R) of Pt(II) complex to spectrin, was induced by the binding of Pt(II) complexes. It indicated that the interaction of both CDDP and cis diaquodiamine platinum(DADP) with SP followed a two step first order kinetic process in the first stage (1 h), and the kinetic constants were determined. In the second stage, the induced conformation change, polymerization and depolymerization of SP were probably involved. It was noticed that in the reaction of SP and Pt(II) complexes with 1,2 cyclohexanediammine isomers as chiral carrier ligand, stereo matching played a more important role than the affinity of Pt(II) to thiol groups of SP.
基金financial support from the National Natural Science Foundation of China(No.21978042)the Fundamental Research Funds for the Central Universities(No.DUT22LAB610).
文摘A novel cationic Pt(Ⅱ)complex 2 with 2-(2,4-difluorophenyl)pyridine as the cyclometalating ligand and 1,10-phenanthroline as the auxiliary ligand has been synthesized and fully characterized.This complex exhibits much higher aggregation-induced phosphorescent emission activity than that of a nonfluorinated complex 1 in CH_(3)CN/H_(2)O.The complex 2 demonstrates efficient detection on picric acid(PA)in CH_(3)CN/H_(2)O,providing a high quenching constant(K_(SV)=2.3×10^(4) L/mol)and a low limit of detection(LOD=0.26μmol/L).In addition,complex 2 shows high selectivity for detection of PA in real water samples.Density functional theory calculations and proton nuclear magnetic resonance spectra suggest that the detection mechanism is attributed to the photo-induced electron transfer.
基金supported by the Open Project of State Key Laboratory of Urban Water Resource and Environment,Harbin Institute of Technology(No.ES202306).
文摘Treatment of precious metals in electronic waste has attracted tremendous attention and is essential for both environmental protection and resource sustainable development.In this study,a novel adsorbent for precious metal ions,V_(2)O_(3)spiny hollow nanospheres(pV_(2)O_(3)SHN),was synthe sized through a one-step hydrothermal-as sis ted methodology for the adsorption of Au(Ⅲ),Ag(Ⅰ),Pd(Ⅱ),and Pt(Ⅳ) from the leaching solution of electronic waste.The results reveal that the p-V2O3SHN hierarchy was successfully constructed with a hollow structure and dense spiny morphology.The prepared p-V2O3SHN can effectively remove precious metal ions such as Au(Ⅲ),Ag(Ⅰ),Pd(Ⅱ),and Pt(Ⅳ),with the selective capture order being Au(Ⅲ)> Ag(Ⅰ)> Pt(Ⅳ)> Pd(Ⅱ)> other metal ions.This superior adsorption capability can be attributed to the multi-diffusible,intermingled composition,and numerous active sites decorating the p-V2O3SHN hierarchy,facilitating the uptake of Au(Ⅲ),Ag(Ⅰ),Pd(Ⅱ),and Pt(Ⅳ) ions from electronic waste.The Langmuir model provided a better fit for the uptake process,revealing maximum uptake capacities of 833.33 mg/g for Au(Ⅲ),370.37 mg/g for Ag(Ⅰ),42.01 mg/g for Pd(Ⅱ),and 77.51 mg/g for Pt(Ⅳ) on p-V_(2)O_(3)SHN.Remarkably,p-V_(2)O_(3)SHN exhibited a robust affinity for the adsorbate due to the presence of surface defects and reduction reactions.The new p-V2O3SHN also demonstrated good reusability for three sorption cycles,highlighting its potential for electronic waste treatment.Due to its facile synthesis and excellent efficiency,hierarchical p-V2O3SHN presents itself as a promising candidate for the selective uptake of Au(Ⅲ),Ag(Ⅰ),Pt(Ⅳ),and Pd(Ⅱ) from electronic waste.
基金This work was financially supported by the Department of International Cooperation and Exchanges in Ministry of Education of China (No. (01)345)
文摘The title complex, [Mn2(O-Py3A)(DPK-CH3O)(CH3OH)]2?2ClO4?4CH3OH (C64H70Cl2- Mn4N12O22, Py3AH = N-(bis(2?-pyridyl)methyl)-2-pyridinecarboxamide, DPK = di-2-pyridyl ketone) has been synthesized and its crystal structure was determined by X-ray diffraction. It crystallizes in the monoclinic system, space group P21/n with a = 12.667(9), b = 16.793(12), c = 17.070(13) ?, β = 100.997(13)o, V = 3565(5) ?3, Dc = 1.537 g/cm3, Mr = 1649.98, Z = 2, μ(MoKα) = 0.851 mm-1 and F(000) = 1696. The final R and wR are 0.0639 and 0.1320, respectively for 3979 observed reflec- tions with I > 2σ(I). In the tetranuclear complex, each Mn(II) atom is six-coordinated and the four Mn(II) atoms are coplanar, exhibiting a parallelogram arrangement; while the deprotonated ligands are oxidized to O-Py3A2- anions and cleaved to DPK-CH3O– anions (the monoanion of mono- methylated diol of DPK) furthermore.
基金This work was supported by the National Natural Science Foundation of China (No. 20371028)and Natural Science Foundation of Tianjin (No. 023605811)
文摘The Cu(II) complex with the ligand 2,9-bis(n-2?5?diazaheptanyl)-1,10-phenan- throline (L) has been synthesized and characterized by single-crystal X-ray diffraction. It crys- tallizes in the monoclinic system, space group P21/n with a = 12.549(4), b = 13.544(4), c = 16.767(5) ? = 107.179(5), C22H32Cl2N6CuO8, Mr = 642.98, V = 2722.5(13) 3, Z = 4, Dc = 1.569 g/cm3, ?= 1.056 mm-1, F(000) =1332, the final R = 0.0733 and wR = 0.1581. The X-ray analysis revealed that the Cu(II) ion is coordinated by six nitrogen atoms of the ligand, in which two nitrogen from phenanthroline and another two from the imine groups near phenanthroline are in the equatorial plane while the two from imine groups at the end of both arms in the axial positions. The coordination geometry can be described as a compressed octahedron.
文摘The platinum (II) complexes of the [Pt (N4,N7-Ribavirin) (DMSO) Cl], [Pt (N4,N7-De-oxyribavirin) (DMSO) Cl] were obtained by the reactions of cis-[Pt (DMSO)2 Cl2] and K[Pt (DMSO) Cl3] with 1-??-D-ribofuranosyl-1,2,4-triazole-3-carboxamide (Ribavirin) and its deoxy-analogue (deoxyribavirin). The preparation of 1-(2'-deoxy-?-D-ribofuranosyl) -1,2,4-triazole-3-carboxamide was also performed through a four-step procedure, protection of 3', 5'-dihydroxyl group of Ribavirin with 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane (TPDS-Cl), phenoxythio-carbonylation of the 2'-hydroxyl group of 3', 5'-O-TPDS-Ribavirin with phenoxythiocarbonyl-chloride (PTC-Cl), reduction of 2′-O-phenoxythiocarbonyl ester of 3', 5'-O-TPDS-Ribavirin with tri-n-butyltin hydride and AIBN, deprotection of 3', 5'-O-TPDS-Ribavirin with tetrabutylammon-ium fluoride in THF.
基金supported by the University Science Foundation of Anhui Province (No. KJ2011Z271)the Applied Chemistry Key Constructing Subject of Anhui Province (No. 200802187C)
文摘An alkaline earth metal-organic framework [Ba（Hsip）（H2O）4]n （1, NaH2sip = 5-sulfoisophthalic acid sodium） has been constructed, and characterized by single-crystal X-ray diffraction. In complex 1, each Ba（II） atom coordinates to one ligand Hsip3- and four water molecules with a distorted nine-coordinated monocapped tetragonal antiprism geometry. Each Hsip2- anion acts as a μ3-bridging ligand, in which two carboxylate groups adopt the same bidentate chelating coordinating model and the sulfonate group takes a monodentate coordinating model, resulting in a wave-like two-dimensional network with a （6, 3） topological structure. The two-dimensional networks are further linked by O–H···O to form a three-dimensional structure. Luminescent property and thermal stability of complex 1 are investigated. 1 belongs to the orthorhombic system, space group Pna21 with a = 7.3333（2）, b = 16.7044（3）, c = 10.4817（2）, Z = 4, V = 1283.99（5）3, Mr = 453.58, Dc = 2.346 g/cm3, F（000） = 880, μ = 3.314 mm–1, the final R = 0.0261 and wR = 0.0592 for 2425 observed reflections with I 2σ（I）.
文摘Oxygenation constants and thermodynamic parameters DeltaH degrees and DeltaS degrees of cobalt (II) complexes with bis-(furaldehyde) Schiff bases (1, 2, 3, 4)were obtained by mearsuring saturated dioxygen uptake of these complexes in pyridine at different temperature. These complexes could activate molecular oxygen and were used as catalysts in cyclohexene oxidation. The influence of ligand structure on the dioxygen affinity and catalytic activity of the complexes were discussed.
基金This work was supported by the National Natural Science Foundation of China (20001007 20131020)+1 种基金and Natural Science Foundation of Fujian Province (2003I031 A0420002)
文摘The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2?-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was determined by single-crystal X-ray diffraction method. It crys- tallizes in triclinic, space group P1, C44H31ClCu2N4O12, Mr = 970.26, a = 8.175(2), b = 16.254(4), c = 16.946(4) ?, α = 62.966(6), β = 84.833(8), γ = 84.348(8)°, V = 1993.4(8) ?3, Z = 2, Dc = 1.616 g/cm3, F(000) = 988 and μ = 1.207 mm-1. The final R = 0.0429 and wR = 0.0843 for 5682 observed reflections with I > 2σ(I). Each copper(II) atom displays a distorted square-pyramidal geometry with two nitrogen atoms of one chelate 2,2?-bipy molecule, two oxygen atoms from two different bridging carboxylate groups of Hpht- and one bridging chloride atom occupying the apical position. The two copper(II) atoms are connected by a μ2-Cl atom and two bridging Hpht- ligands in a syn-syn coordination mode to form an isolated dinuclear unit. The molecular structure is extended to a one-dimensional wavy chain through hydrogen bonds. The title complex exhibits blue fluorescent emission at 443 nm (λex = 372 nm) in the solid state at room temperature.
基金supported by the Science and Technology Research Projects of the Education Department of Jilin Province (No. 2011. 459)
文摘A new metal-organic complex Zn2（cbba）4（phen）2 （Hcbba = 2-（4＇chlorine-ben- zoyl）benzoic acid, phen = 1,10-phenanthroline） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence spectrum and single-crystal X-ray diffraction. The compound crystallizes in orthorhombic, space group Pbcn with a = 12.0821（II）, b = 18.3140（17）, c = 30.961（3） A, V= 6850.7（11） A^3, C80H48C14N4O12Zn2, Mr= 1529.76, Dc = 1.483 g/cm^3,μ（MoKa） = 0.925 mm^-1, F（000） = 3120, Z = 4, the final R = 0.0559 and wR = 0.1146 for 3963 observed reflections （I〉 2σ（I））. In the crystal structure, the zinc atom is five-coordinated with three carboxylate oxygen atoms from three different cbba ligands and two nitrogen atoms from the phen ligand, showing a distorted square-pyramidal geometry. Furthermore, it exhibits a 3D supramolecular network through π-π interactions and shows yellow photoluminescent property at room temperature.
基金Supported by the Natural Science Foundation of Zhejiang Province (Y407301)
文摘A new mixed-ligand nickel（Ⅱ） complex, [Ni（L）（DCA）（H2O）]·2H2O （L = C8H9N3, 2-aminomethyl-benzimidazole, DCA2- = 7-oxabicyclo[2,2,1]heptane-2,3-dicarboxylate, demethylcantharate, C8H8O5）, has been synthesized and characterized. The structure of the complex was determined by single-crystal X-ray diffraction. It is of monoclinic system, space group P21/c with a = 7.7211（7）, b = 12.0799（12）, c = 19.7867（19）, β = 100.390（6）°, V = 1815.2（3） nm3, Dc = 1.625 g·cm-3, Ζ = 4, F（000） = 928, R = 0.0314 and wR = 0.0822. In addition, the interaction between the complex and DNA was studied by means of fluorescence spectra and viscosity. The results indicate that the complex binds to DNA by the mode of partial intercalation with the Stern-Volmer constants Ksv of 3.81 × 104 mol·L-1.
基金National Basic Research Program of China (Grants No. 2009CB940903 and 2009CB918502)the National Natural Science Foundation of China (Grant No. 20721003 and 81025017)National S&T Major Projects (Grant No. 2012ZX09103-101-072).
文摘A convenient and efficient method for the preparation of α-substituted β-amino acids has been developed by reacting compound 2 with various boric acid/borate 3 through Suzuki coupling reaction,which gave multiple structure types of substituted Ni（II） complexes 4 in high yields.Hydrogenation and hydrolysis of complexes 4 led to the corresponding α-substituted β-amino acids.
基金This work was financed by the National Key Fundamental Research Program of China.
文摘A new zinc(II) complex, Zn(2-NH2py)2Br2 (py=pyridine), has been synthesized, and its molecular structure has been confirmed by IR, elemental analysis and -ray crystal structure analysis. Its space group is P21/n with Mr=413.43 (C10H12Br2N4Zn), a=7.435(2), b=12.865(3), c=14.186(4)? b=94.08(2)? V=1353.5(5) 3, Z=4, Dc=2.029 g/cm3, F(000)=328, ?2.378mm－1, R=0.0283, wR=0.0501. The total observed reflections with I≥2?I) were 5314, of which the independent reflections were 3106. The complex structure contains a distorted tetrahedron formed by four atoms coordinated to zinc atom, namely two bromide atoms and two nitrogen atoms. The two ZnBr bond lengths within one molecule, 2.3763(6) and 2.4002(5)? respectively, are not equal; and so are the two ZnN bond lengths, which are 2.031(2) and 2.044(2)?respectively. The calculation results using PM3 method through MOPAC software package in Chem 3D show that its first molecular hyperpolarizability b value is 5.210－30esu, which is comparable with that of p-nitroaniline. No bulk SHG effect has been detected due to the centrosymmetric space group.
基金Supported by the Science and Technology Research Projects of the Education Office of Jilin Province (No. 2009. 272)
文摘A new dinuclear complex [Zn（dpa）（bipy）（H2O）]2 （dpa = 2,2＇-diphenic acid, bipy = 2,2＇-bipyridine） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence spectrum and single-crystal X-ray diffraction. The complex crystallizes in monoclinic, space group P21/c with a = 10.960（2）, b = 9.4841（18）, c = 20.599（4）, β = 104.452（3）o, V = 2073.4（7）3, C48H36N4O10Zn2, Mr = 959.55, Dc = 1.537 g/cm3, μ（MoKα） = 1.225 mm-1, F（000） = 984, Z = 2, the final R = 0.0364 and wR = 0.0843 for 2788 observed reflections （I 〉 2σ（I））. In the crystal structure, the zinc atom is five-coordinated with two carboxylate oxygen atoms from different dpas, one coordinated water molecule and two nitrogen atoms from bipy ligands, showing a slightly distorted triangular bipyramidal geometry. Furthermore, it exhibits a zero-dimensional network structure with a sixteen-membered ring and shows yellow photoluminescent property at room temperature.
基金Supported by the Natural Science Foundation of Hunan Province(No.11JJ9006)Key Project of Science and Technology Plan of Hunan Province(2012FJ2002)the Construct Program of the Key Discipline in Hunan Province
文摘A new copper complex 2{Cu（C10H8N2）[C8H11O2（COO）]（H2O）3}·（H2O）5 with bicycle[2.2.1]hept-2-en-5,6-dicarboxylic acid（H2L） [C7H8（COOH）2], basic copper carbonate and 2,2＇-bipyridine has been synthesized in the mixed solvents of methanol and water. It crystallizes in the triclinic system, space group P1, with a = 7.4626（5）, b = 11.9779（8）, c = 12.9841（8）A, α = 109.7040（10）, β = 98.7550（10）, γ = 90.6240（10）°, V = 1077.50（12）A3, Dc = 1.538 g/cm^3, Z = 1, F（000） = 520, GOOF = 1.065, R = 0.0360 and wR = 0.0950. The copper ion is coordinated with four oxygen atoms from one H2 L molecule and three water molecules together with two nitrogen atoms from the 2,2＇-bipyridine molecule, forming a distorted octahedral coordination geometry. The thermal stability and electrochemical properties were also studied.
